30 January 2015 1K UV-A Automotive Refinish; Clear Coats and Primers Michael J. Dvorchak Phone: 404-719-8912 E-Mail: Michael.Dvorchak@allnex.com www.allnex.com 1 Introducing Allnex! 2 Outline • Changes in the automotive OEM and refinish markets • Introduction of UV-A curable auto refinish • Current products and innovation in the market • Future outlook for the UV–A curable refinish market • Conclusions • References • Questions 3 Changes in the Automotive OEM and Refinish Markets • Major changes in polymers technologies used in coatings • NC lacquers were acceptable when the only color option was black • 2 K reactive primers, clear coats, water based “base coats” • Lower VOC and VHAPS • Major changes in substrate technologies • • • • Cold rolled steel Engineered plastics Aluminum Composites NC lacquers Base Coat; smokey quartz 4 Introduction of UV–A Auto Refinish • Early attempts to develop a UV refinish clear coat (2K) 1 • UV Flash lamp (Xe lamp @ 480 nm) used in conjunction with BAPO PI • Polymer chemistry was dual cure (R-N=C=O; R-C=C & R-OH) • Cure took place with 10 to 20 flashes • Patent application on a UV-A primer in 2001 (1K) 2 • UV A lamp source was 250 W iron doped source filtering out UV B, UV C • Polymer chemistry was mono-cure (R-C=C) • Cure took place in several minutes leaving an uncured surface due to oxygen inhibition • Solvent wipe required Photo provided by I-CAR 5 Introduction of UV–A Auto Refinish • Automotive OEM technical paper on UV auto refinish clear coats 3 • OEM evaluates UV cure clear coats • HALS and UVAs were formulated into these clear coats • OEM found that these systems embrittled to unacceptable levels under accelerated weathering • 2003 Patent application by a paint company on UV–A (1K) CC 4 • • • • UVA/UVV & UV–A only curable Polymer chemistry was mono-cure (R-C=C) Cure times were 4 minutes with no surface inhibition No gloss reduction or cracking was found when subjected to SAEJ1960 6 Introduction of UV–A Auto Refinish • 2003 RADTECH report on use of UV–A cure primer systems in body shops 5 • The following benefits were noted in the report: 1) time savings of 25 to 88 % on each job, 2) less preparation time, 3) use of disposable utensils is reduced, 4) less masking, 5) no flash times required between layers and 6) less waste over a 2K system • Report states the need for a UV–A clear coat • 2005 OEM/Refinish paint company awarded the US Presidential Green Chemistry award for UV-cured auto finishing paint Photo provided by I-CAR 7 Introduction of UV–A Auto Refinish • 2006 patent application on dual cure UV clear coat spot repair 6 • UV–A light source used for cure • Polymer chemistry was dual cure (R-N=C=O; R-C=C & R-OH) • After cure, the surface was easily polishable without defects • 2006 patent filed by an auto OEM paint company on a UV–A primer that has a high pigmentation levels and extremely low oxygen inhibition 7 • • • • Uses a 400 W UV–A light that is held 10 to 30 cm away from the substrate Chemistry is a mono-cure technology (R-C=C) Cure time is 1-3 minutes at a thickness of 200 microns Patent reports the ability to sand the primer after UV curing and the coating has had time to cool 8 Introduction of UV–A Auto Refinish • Auto OEM technical paper on scratch performance of three UV cure automotive refinish clear coats 8 • Three UV cure clear coats tested against a thermally cured acrylic/melamine/silane clear coat. • Car wash performance testing by the AMTEC-Kistler showed that two of the UV cure clear coats performed better than the acrylic/melamine/ silane clear coat. 9 Introduction of UV – A Auto Refinish • Patent filed in 2007 that uses a structure to cure the UV paint 9 • Patent publication filed in 2009 on a UV cure spot blender for clear coats 10 • Uses a UV–A 400 lamp to cure the UV clear coat • Chemistry is based on 2K dual cure or 3K dual cure thiolene-based technology • Clear coat technology is cured for 5 minutes at a distance of 10 inches Photo provided by I-CAR 10 Introduction of UV – A Auto Refinish • OEM awarded the 2010 RADTECH Emerging Technology Award for the use of an in-line UV spot repair 11 • The UV cure technology could possible reduce their cycle time by 50% • OEM evaluating the process to see if this technology will meet the durability specifications and test protocols. • Facilities would have to be modified to use the UV cure technology Photo provided by I-CAR 11 Current Products and Innovation in the Market High throughput formulation screening 12,13 1:1 Resin/ 50:50 blend Symplex lattice design Delta Fox Trot Echo Hotel Charlie Delta/Fox Trot Delta/Echo Delta/Charlie Fox Trot/Echo Fox Trot/Echo Fox Trot /Hotel Fox Trot / Charlie Echo / Hotel Echo / Charlie Hotel / Charlie Reactive diluent [PI] Photoinitiator/blend HDDA Irgacure 184 # 4% TPGDA Irgacure 500 # 1% TMPTA Irgacure 500 #/Amine synergist Darocur 1173 # CGI 1870 # Irgacure 819 # Irgacure 1850 # Darocur 4265 # Irgacure 184/Darocur 1173 Genacure ITX + Irgacure500/Amine synergist/Irgacure 819 Genacure ITX/ CGI 1870 Irgacure 1300 # Irgacure 1700 # Irgacure 2959 # D-optimal design including 2nd order interactions: ~ 500 formulations and ~ 24,000 films (5 weeks of experimentation) # BASF, + Rahn Irradiation time [sec] 0 8 20 4 60 180 Distance from lamp Current Products and Innovation in the UV-A Refinish Market Echo/Hotel Echo/Charlie Echo Hotel/Charlie Hotel Fox Trot/Echo Fox Trot/Hotel Fox Trot/Charlie Fox Trot Delta/Echo Delta/Hotel Delta/Fox Trot Delta/Charlie Delta Charlie 1870 1173 1870/ITX ITX 4265 1700 1300 184/1173 184 2959 1850 500/Amine 500 819 500/819/Amine The larger the bubble shows the least amount of surface inhibition after UV cure Current Products and Innovation in the Market Photo micrograph of a blend line for a commercially available UV – A curable clear coat over a black base coat 14 Current Products and Innovation in the Market Concept of matching the Tg’s of traditional 2 K clear coat technology with a 1K UV A cure clear coat 14 Resin °C UA Resin A UA Resin B UA Blend 1 UA Blend 2 UA Blend 3 UA Blend 4 UA Blend 5 Commercial UV Refinish Commercial 2K Refinish 10 104 103 105 106 84 74 101 62 isocyanurate allophanate O O R O N N N R R O O N O N H 1 2 O R= -(CH2)6 N H O intramolecular H-bridge R R O O O O 15 Current Products and Innovation in the Market Blend line Blend line Photo micrograph of a blend line for a commercially available 2K Clear Coat over a black base coat Photo micrograph of a blend line for a UV – A Cure Clear Coat After matching Tg of a 2K Clear Coat over a black base coat 16 Current Products and Innovation in the Market Photograph of a 1K UV-A primer and a 1K UV-A Clear Coat after 8 years of service in the NE US Photograph of a 2K traditional primer and Clear Coat that was used as the standard for testing on the same vehicle 17 Future Outlook for the UV–A Curable Refinish Market • Driving Change event in 2003 15 • Over 130 industry personnel attended • The future looked bright over 10 years ago • RADTECH Transportation Focus Group & I-CAR • In 2007 RADTECH ( industry trade organization) teamed up with I-CAR (auto refinish professional training organization) to develop a web based training module devoted to UV-A auto refinish • Since this launch over 900 professional body repair technicians have paid to take this unique training program • The future of 1K UV–A cure is tied to the introduction of a 1K UV-A cure clear coat 16 Photo provided by I-CAR 18 Conclusions • A significant amount of work has been done trying to develop the market for 1K UV-A Primers and Clear Coats • When polymer technology went from NC lacquers to 2K reactive system, there was a lot of resistance to change • The difficulty to repair was the major resistance to change from NC lacquers to a 2K reactive system • In time better acceptance of the 1K UV-A Primers and Clear Coats will occur 19 References 1.) K.Magg, et al., Progress in Organic Coatings 40 (2000) 93-97 2.) D. Fenn, et al., US 6,838,177 Mar. 27, 2003 3.) M. Nichols, et al., RADTECH Report Nov/DEC 2001 4.) D. Braun, et al., US 2005/0095371 May 5, 2005 5.) D. Maloney, RADTECH Report NOV/DEC 2003 6.) B. Lettmann, et al., US 7,683,105 Mar. 23, 2010 7.) J. O’Neil, US 8,227,050 Jul. 24, 2012 8.) C. Seubert, et al., J. Coat. Technol. Res., 4 (1) 21-30, 2007 9.) K. DeRegge, et al., US 7,704,564 Apr. 27, 2010 10.) M. Bowman, et al., US 2011/0097481 Apr. 28, 2011 11.) Ford Motor Company, 2010 Emerging Technology Award, RADTECH 2010 Conference 12.) H. Bach, et al., RADTECH Europe, Nov. 2003 13.) S. Strazisar, et al., RADTECH Report, Nov. 2003 14.) M. Jeffries, et al., RADTECH 2/5 2006, Apr. 2006 15.) RADTECH NA sponsored event; Driving Change, Sept. 2003 16.) H.-B. Gia, WO 2009/039137 Mar. 26, 2009 20 Thank you for your attention! For more information, please visit us at www.allnex.com. Contact Name: Cell Phone: E-mail: www.allnex.com Michael J. Dvorchak 404-719-8912 Michael.Dvorchak@allnex.com www.allnex.com Notice: Trademarks indicated with the ®, ™ or * are registered, unregistered or pending trademarks of Allnex IP S.à r.l. or its directly or indirectly affiliated Allnex Group companies. Disclaimer: Allnex Group companies (“Allnex”) decline any liability with respect to the use made by anyone of the information contained herein. The information contained herein represents Allnex's best knowledge thereon without constituting any express or implied guarantee or warranty of any kind (including, but not limited to, regarding the accuracy, the completeness or relevance of the data set out herein). Nothing contained herein shall be construed as conferring any license or right under any patent or other intellectual property rights of Allnex or of any third party. The information relating to the products is given for information purposes only. No guarantee or warranty is provided that the product and/or information is adapted for any specific use, performance or result and that product and/or information do not infringe any Allnex and/or third party intellectual property rights. The user should perform its own tests to determine the suitability for a particular purpose. The final choice of use of a product and/or information as well as the investigation of any possible violation of intellectual property rights of Allnex and/or third parties remains the sole responsibility of the user. ©2015 Allnex Belgium SA. All Rights Reserved. Back Up Slides Light Output Readings After UV A Cure Refinishing of PC • 1993 Dodge Sundance • Readings at low audit settings • High beam 17,000 Candla • Prior value = 7,000 Candla • Low beam 7,000 Candla • Prior value = 3,000 Candla Many military equipment / vehicles use polycarbonate as replacement for glass due to its performance for bullet resistance and light weight. Stencil UV A Coating F-16 C-130; Small Area Repair UV A Military Applications UV A Cure Battle Field Composite Repair • KISS Principle • Ballistic holes in composites - AK-47 or shrapnel • Quick return to service • Simple and quick process that returns the aircraft to service with eventual permanent repair at the depot • Commercial air lines interested is this technique for remote location repair Basics of UV Curing Curing of Coatings with electromagnetic radiation Curing conditions seconds/ milliseconds UV- or electron beam curing Source: Bürkle Electron beam < 1 nm X- Rays < 100 nm UV-C 100 - 280 nm Imperative for the polymerization of printing inks and varnishes for a complete curing. UV light < 400 nm wave length UV-B 280- 315 nm Supports and maintains the triggered off reactions and ensures a better curing because of longer waves. Visible light > 400 nm IR > 800 nm UV-A 315 - 380 nm Responsible for the curing of very thick layers Low Energy UV-A Lamps Philips TL03 Promotor Car 250 Honle 250 Panacol 250 UV Process Supply 400 H&S Autoshot 400 Low Intensity Microwave Lamp • Quantum Technologies • Low powered lamps • Current UV-A lamp assembly has a series of bulbs from 320 to 400 nm • Bulbs can be made to desired wavelength output NEW UV-A Light Sources Automotive Refinish/Aerospace & Printing • 1,200 W UVA Light • LED UVA • H & S Auto Shot • Phoseon Technology